Oil-soluble carbonated metallo alkylated aryl sulfonates and compositions containing the same



United States Patent O M 2,916,451 OIL-SOLUBLE CARBONATED METALLO ALKYL- ATED ARYL SULFONATES AND COMPOSI- TIONS CONTAINING THE SAME Harry W. Faust, St. Louis, Mo., assignor to Monsanto Chemical Company, St. Louis, Mo., a corporation of Delaware No Drawing. Application December 18, 1952 Serial No. 326,790 25 Claims. (Cl. 25233.4)

This invention relates to new and improved mineral oil fraction-containing compositions. More particularly it relates to mineral oil fractions of lubricating viscosity containing a blend of an oil-soluble carbonated product obtained by treating a basic barium salt of a long chain alkyl substituted aryl sulfonic acid with carbon dioxide and an oil-soluble phosphorizedand sulfurized-dicyclic terpene.

Oil-soluble metallo alkylated aryl sulfonates have been proposed for use in mineral oil fractions such as motor fuels, diesel fuels, fuel oils, lubricating oils, etc. as detergents in order to disperse sludge formations. While these sulfonates are very effective detergent-dispersants they tend to increase the oxidation rate of the oil thus increasing the amount or concentration of acidic oxidation products in the oil, which in addition to a clogging problem presents a serious corrosion problem. Among the commonly used oxidation inhibitors for mineral oil fractions are the oil-soluble sulfurizedand phosphorizeddicyclic terpenes and while they are highly effective in preventing or inhibiting the formation of oxidation products during the storage or the use of the oil, their antioxidant efiiciency is reduced when they are employed in conjunction with oil-soluble metallo alkylated aryl sulfonate detergent-dispersants. In other words While the aforementioned detergent-dispersants and antioxidants perform their individual functions in a highly satisfactory manner in mineral oil fractions, as for example in fuel oils and in lubricating oils, the two separate additives do not cooperate to produce an entirely satisfactory antioxidant and detergent-dispersant when used together.

In accordance with this invention it has beenfound that the oil-soluble carbonated product obtained upon reacting an oil-soluble basic barium salt of long chain alkyl substituted aryl sulfonic acid with carbon dioxide when admixed with an oil-soluble sulfurizedand phosphorized-dicyclic terpene in a mineral oil fraction such as a motor fuel, a naphtha, a diesel fuel, a lubricating oil, etc., produces a highly stable and improved mineral oil fraction-containing composition. The products formed by reacting the basic barium sulfonate reactant with carbon dioxide are believed to be carbonates, however, they are of a complex nature and because of this it is not possible to state their chemical structure with absolute certainty. Hereinafter they will be referred to as carbonated products.

The basic barium salts of long chain alkyl substituted aryl sulfonic acid reactants employed in making the detergent-dispersants of this invention are of unknown structure, however, it is possible that they may be represented by one or both of the following formulae:

wherein R is a long chain alkyl substituted aromatic hydroearbon residue. In the second of the above formulae the colon indicates that the barium contributes both electrons to form a Werner co-ordination compound. It is to be understood, however, that the above structural 2,916,451 Patented Dec. 8, 1959 ICC formulae are merely those which have been postulated on the basis of analytical results and it is not intended that they in any manner should limit the scope of the invention.

The long chain alkyl substituted aryl sulfonic acids employed in making the above described basic barium hydrocarbon sulfonate reactant of this invention may be represented by the formula RSO H wherein R is a long chain alkyl substituted aromatic hydrocarbon residue. Among the aromatic hydrocarbon nuclei contemplated are such radicals as phenyl, tolyl, ethylphenyl, cumyl, isobutylphenyl, tert. butylphenyl, xylyl, cymyl, biphenylyl, indenyl, naphthyl, and the like. By a long chain alkyl substituent is meant an alkyl radical containing at least 8 carbon atoms. Although any long chain alkyl substituent is contemplated, it is preferable that the substituent be a wax residue and preferably a wax residue having a chain of 20 to 30 carbon atoms. From a practical standpoint it has been found that the aromatic hydrocarbon nucleus of the sulfonic acids (R-SO H) employed in preparing the reactants of this invention should contain not more than four long chain alkyl substituents. In general, however, those sulfonic acids wherein the aromatic hydrocarbon nucleus contains 1-3, inclusive, long chain alkyl substituents, are preferred in the preparation of the reactants of this invention and it is particularly preferred that they contain but two long chain alkyl substituents.

The detergent-dispersants of this invention are prepared by dissolving a basic barium salt of a long chain alkyl substituted aryl sulfonic acid in an inert organic solvent, e.g. Stoddards solvent, reacting therewith carbon dioxide, separating the water by-product produced thereby, and isolating the desired carbonated product. In that the basic barium long chain alkyl substituted aryl sulfonate reactantsare highly soluble in mineral oil fractions of lubricating viscosity of the type normally used in internal combustion engines it has been found convenient in preparing compositions for use in crank case lubricants to dissolve the basic barium sulfonate reactant in such mineral oils in order to form a concentrate of the sulfonate, e.g. 25-75% by weight of the sulfonate reactant, and bubble carbon dioxide through the concentrated solution at temperatures from 20-150 C. The incorporation of carbon dioxide in the mineral oil solution of the sulfonate reactant does not produce a less soluble product and as a result detergent-dispersant containing lubricating compositions can be prepared in concentrates, e.g. 25-75% by weight, of the carbonated product.

As exemplary of a basic barium salt of an alkylated aryl sulfonic acid, its carbonated product and the preparation of same, the following is illustrative:

EXAMPLE I A parafiin wax having an average of about 23 carbon atoms in the molecule and an ASTM melting point of about 125-127 F. is chlorinated at about -85 C. with gaseous chlorine until the weight of the wax is increased to about 12%.

1000 parts by weight of the so prepared chlorowax is fed into a suitable reaction vessel containing a mixture of 201 parts by Weight of benzene and about 36 parts by weight of aluminum chloride catalyst over a period of 3-4 hours at a temperature maintained at 35-50 C. Thereupon the temperature of the reaction mix is raised to -90" C. and is held there for 2 hours. The catalyst sludge is removed and the unreacted benzene and other contaminants are separated from the sludge-free liquid by steam distillation. The product obtained upon removing the residual water is a diwax-alkylated benzene.

To 1000 parts by weight of the diwax-alkylated benzene so prepared is added over a 3 hours period approximately 459 parts by weight of 25% oleum while maintaining the temperature at 4555 C. Upon completion of the acid addition there is added approximately 105 parts by weight of water while maintaining the temperature at 5055 C. Thereupon 1000 parts by weight of SAE-lO grade mineral oil is added to the mix while raising the temperature to 7075 C. The reaction mixture of acid and oil is then stirred for about 30 minutes at about 75 C. Upon stopping the agitation the oily layer is separated from the aqueous layer by draining off the latter.

2129 parts by weight of the mixture of mineral oil and the diwax-alkylated benzene sulfonic acid obtained by the aforementioned draining operation is then placed in a suitable reaction vessel, and thereto is added about 509 parts by weight of barium hydroxide octahydrate. Upon completion of the addition the mix is heated to 80-90 C., and agitated at that temperature for 30 minutes.

Thereupon the mix is heated to about 125 C. and the water distilled off. Vacuum is then applied to complete the dehydration. The dehydrated mixture is then admixed with a small amount of clay and the mixture filtered through a press at 100-110 C. 2376 parts by weight of approximately a 58% by weight solution of the basic barium salt of a diwax-alkylated benzene sulfonic acid is obtained. The blend of oil and sulfonate upon analysis is found to contain about 9.4% barium.

Upon diluting this 58% by weight mineral oil concentrate of sulfonate with 2064 parts by weight of mineral oil (SAE-lO grade motor oil) there is obtained approxi- .mately a 31% by weight solution assaying about barium, about 1.2% sulfur and possessing a sp. gr. of 0.96 at 60/60 F. and a Saybolt viscosity of 65 at 210 F. This product is characterized by exceptional detergent properties.

EXAMPLEII At reduced pressure and at a temperature of 120-135 .0. carbon dioxide is bubbled at the rate of about 0.81.0

pound of CO per min. into 1000 parts by weight of the 31% mineral oil solution of the basic barium salt of the diwax-alkylated benzene sulfonic acid of Example I for about 3 hours. Upon stopping the carbon dioxide addition the temperature is maintained at 105-135 C. and vacuum is applied in order to complete the removal of the water by-product. The reaction product is admixed with a small amount of clay and the mixture filtered through a press. The resultant product is approximately a 31% solution possessing a sp. gr. of 0.96 at 60/60 F. and a Saybolt viscosity of 65 at 210 F. and upon analysis is found to contain about 5% barium and about 1.2% sulfur. The amount of carbon dioxide absorbed in the resultant composition is about 8.1 parts by weight or approximately 1 mol of carbon dioxide per 2 mols of the basic barium salt of the diwax-alkylated benzene sulfonic acid. The amount of water by-product produced is about 1 mol per mol of carbon dioxide absorbed.

The oil-soluble sulfnrizedand phosphorized-dicyclic terpenes of this invention are those obtained by reacting a dicyclic terpene, such as pinene, camphene, fenchene and similar terpenes containing one double bond in the molecule and comprising two ring systems, with a phosphorus sulfide at a temperature of about 100-160 C. While any phosphorus sulfide such as P 5 P 8 P 8 P 8 P 8 etc., can be employed in the preparation of said reaction products, the preferred reaction products are those obtained employing phosphorus pentasulfide (P 8 While the proportions of these reactants will vary depending upon the oil-solubility and oil-improvement properties desired the preferred product is that obtained by the reaction of about one mol of a phosphorus sulfide, e.g. P 8 with A mixture of 245 parts by weight of pinene (substantially 1.8 mols) and 220.5 parts by weight of mineral oil (SAE-lO grade motor oil) is charged into a suitable reaction vessel and is heated to 110115 C. While stirring, parts by weight of phosphorus pentasulfide (substantially 0.45 mol) are added slowly while maintaining the temperature at 120 C. The temperature of the mixture is then increased to about 150 C. and stirred at that temperature for one hour. After partial cooling of the reaction mixture there is added a small amount of clay and the mixture filtered. The filtered product is a clear red viscous oil, having a sp. gr. of 1.02 at 15.6/15.6 C., a Saybolt viscosity of at 210 F. and analyzing about 4.7% phosphorus and about 13% sulfur.

As exemplary of the improved properties of the new lubricating compositions the following compositions containing 0.65% by weight of a sulfonate detergent and 0.34% by weight of a phosphorizedand sulfurized-dicyclic terpene are prepared and evaluated in a CRC Designation L-4 -545 (described on page 394 of the CRC -Mineral oil (51113-30 grade Handbook 1946) engine test for oxidation stability:

Lubricant Composition A B (Parts by weight) (Parts by weight) Product of Example I (31% {0.65 sulfonatc solution). 1.45 mineral oil.

0.65 carbonated snlionatc Product of Example II (31% 1.45 mineral 011. 0.34.

solution).

Product of Example III (mineral oil solution of the P 8 pinene reaction product containing 4.7% phosphorus and 13% sulfur).

Oxidation inhibitor activator (commercial) 97.31. motor oil).

Table I Lubricant Lubricant A B Bearing corrosion (mgs. weight loss in metal per bearin Piston varnish rating (based on 10) Overall engine rating (based on 100) 9 fIfDC:

pan-

Lubricant Composition 0 D (Parts by weight) (Parts by weight) Product of Example I (31% {0.65 suli'onate solution). 1.45 mineral oil...

0.65 carbonated Product of Example II (31% sulionate.

. solution). 1.45 mineral 011. Product of Example III (min- 0.34 .34.

eral oil solution of a P|Srpinene reaction product containing 4.7% phosphorus and 13% sulfur). Oxidation inhibitor activator 0.40 0.40.

(commerei a1) Mineral oil (SAE-30 grade 97.16 07.16.

motor oil).

Table II Lubricant C Lubricant D Percent Percent Carbon deposit 11 top ring 32 Trace 10 None groove Lacquer deposit.

Table III (Parts by weight) (Parts by weight) Product of Example I (31% {23.8 sulfonate solution). 53.1 mineral oil Product of Example II (31% solution).

Product of Example III (mineral oil solution of 2. P 8 pinene reaction product containing 4.7% phosphorus and 13% sulfur).

sulfonate. 53.1 mineral oil. 23.1.

{23.8 carbonated Composition E on standing at room temperature for 2 hours began to emit hydrogen sulfide and subsequently set up into a gel. Composition F after standing 8-10 weeks still retained its fluid characteristics and did not evolve hydrogen sulfide. Composition F is much superior to Composition E in antioxidant and detergent dispersant properties.

Generally in practicethe new lubricating and fuel compositions of this invention will contain 0.1 to by weight of the carbonated product obtained upon reacting a basic barium salt of a long chain alkyl substituted aryl sulfonic acid with carbon dioxide, but concentrations of 1-3% are satisfactory for most purposes. The concentration of the oil-soluble phosphorized-and sulfurized-dicyclic terpene ordinarily will vary from 0.1- 3% by weight but in general 0.31% is satisfactory. It is to be understood, however, that mineral oil fractioncontaining concentrates are also contemplated herein as for example those mineral oil fraction solutions containing 1040% by weight of the carbonated product of a basic barium salt of a long chain alkylated aryl sulfonic acid and 340% by Weight of a phosphorizedand sulfurized-dicyclic terpene. As exemplary of such concentrate solutions is one containing a 5:212 ratio of a mineral oil fraction to a phosphorizedand sulfurizeddicyclic terpene to the oil-soluble carbonated product obtained by reacting the basic barium salt of a diwaxalkylated benzene sulfonic acid with carbon dioxide.

Such a concentrate is particularly useful in the stabilization of mineral oil fraction used as fuel oils "and diesel fuels.

Employing other alkyl halides than the chlorowax of Example I, which contain at least 8 carbon atoms and preferably not more than 30 carbon atoms as for example decyl chloride chlorkerosene, hexadecyl chloride, octadecyl chloride, etc. in the alkylation of an aromatic hydrocarbon such as benzene, toluene, cumene, xylene, diphenyl, naphthalene, etc., sulfonating the alkylated aromatic hydrocarbon, forming the basic barium sulfonate, and carbonating the latter in the manner set forth in Examples I and II there are produced other homologous oil-soluble carbonated products exhibiting highly satisfactory dispersant-detergent properties which when employed in a mineral oil fraction, such as one of lubrieating viscosity or one useful as a fuel, in conjunction with an oil-soluble sulfurizedand phosphorized-dicyclic terpene antioxidant form a stable mix and a highly effi- .phoric acids, the phenol sulfides, and the sulfurized mono- 6 cyclic terpenes may be also incorporated in the new mineral oil fraction-containing compositions.

The mineral oil fractions employed in making the new lubricating composition of this invention are usually petroleum oils of lubricating Viscosity, that is those straight mineral lubricating oils of the type normally used in-internal combustion engines. However, distillates derived from paraifinic, naphthenic, asphaltic or mixed base crudes, as well as spindle oil and cylinder stocks are also useful as base stocks.

While the invention has been described in reference to mineral oil fractions of lubricating viscosity it is to be understood that the properties of mineral oil fractions employed as fuels, such as the liquid hydrocarbon distillates are also markedly improved by incorporating there in a mixture of an oil-soluble carbonated product obtained from carbon dioxide and a basic barium salt of a long chain alkyl substituted aryl sulfonic acid and an oilsoluble sulfurizedand phosphorized-dicyclic terpene of the types heretofore described. By hydrocarbon distillate fuels is meant those liquid fuels employed in burner systems, diesel and combustion engines and the like which possess a normal distillation range of 300-700 F.

This application is a continuation-in-part of my copending application Serial No. 203,793 filed December 30, 1950, now abandoned, and is a continuation-in-part of my co-pending application Serial No. 326,133, filed December 15, 1952, now abandoned, which latter application is a continuation-in-part of application Serial No. 203,226, filed December 28, 1950, now abandoned.

What is claimed is:

1. A composition comprising a mineral oil fraction having in admixture therewith 0.1-40% by weight of an oil-soluble phosphorizedand sulfuriZed-dicyclic terpene, obtained by reacting substantially one mol of a phosphorous sulfide with substantially four mols of a dicyclic terpene at -160 C., and 0.1-40% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a long chain alkyl substituted benzenoid hydrocarbon sulfonic acid in which the long chain alkyl substituents do not exceed a total of 4.

2. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.1-40% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of a dicyclic terpene at 100160 C., and 0.1-40% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a long chain alkyl substituted benzene sulfonic acid in which the long chain alkyl substituents do not exceed a total of 3 and which alkyl substituents respectively contain 8 to 30 carbon atoms.

3. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.1-40% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of a dicyclic terpene at 100160 C., and 0.1-40% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzenoid hydrocarbon sulfonic acid in which the wax substituents do not exceed a total of 3.

4. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.1-40% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of a dicyclic terpene at 100-160 C., and 0.1-40% by 7. weight. of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzene sulfonic acid in which the wax substituents do not exceed a total of 3.

5. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.1-3% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of a dicyclic terpene at 100160 C., and O.l-l% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzene sulfonic acid in which the wax substituents do not exceed a total of 3.

6. A lubricating composition comprising a mineral oil fractionhaving in admixture therewith O.l-3% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of a dicyclic terpene at 100-l60 C., and 0.1-% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of car- .bon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid.

7. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.13% by weight of an oil-soluble phosphorizedand sulfurized-pinene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of pinene at 100160 C., and 0.1l0% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid.

8. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.13% by weight of an oil-soluble phosphorizedand sulfurized-pinene obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of pinene at 100160 C., and 0.1-10% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid, said wax substituents respectively containing to carbon atoms.

9. A lubricating composition comprising a mineral oil fraction having in admixture therewith 0.31% by weight of an oil-soluble phosphorizedand sulfurized-pinene obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of pinene at 100160 C., and 13% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid, said wax substituents respectively containing 20 to 30 carbon atoms.

10. A fuel oil comprising a hydrocarbon distillate fuel having in admixture therewith O.13% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of a dicyclic terpene at 100160 C., and O.l10% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzene sulfonic acid in which the wax substituents do not exceed a total of 3.

11. A fuel oil comprising a hydrocarbon distillate fuel having in admixture therewith 0.l-3% by weight of an oil-soluble phosphorizedand sulfurized-dicyclic terpene, obtained by reacting substantially one mol of phospho rous penta-sulfide with substantially four mols of a dicyclic terpene at 160 C., and 01-10% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid.

12. A fuel oil comprising a hydrocarbon distillate fuel having in admixture therewith 0.13% by weight of an oil-soluble phosphorizedand sulfurized-pinene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of pinene at 100- C., and 0.140% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid.

13. A fuel oil comprising a hydrocarbon distillate fuel having in admixture therewith 0.31% by weight of an oil-soluble phosphorizedand sulfurized-pinene, obtained by reacting substantially one mol of phosphorous pentasulfide with substantially four mols of pinene at 100- 160 C., and 13% by weight of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid, said wax substituents respectively containing 20 to 30 carbon atoms.

14. A composition comprising a mineral lubricating oil and 0.25 to 25% by weight based upon the oil of the oilsoluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a long chain alkyl substituted benzenoid hydrocarbon sulfonic acid in which the long chain alkyl substituents do not exceed a total of 4.

15. A composition comprising a mineral lubricating oil and 0.25 to 25% by weight based upon the oil of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a long chain alkyl substituted benzene sulfonic acid in which the long chain alkyl substituents do not exceed a total of 3 and which alkyl substituents respectively contain 8 to 30 carbon atoms.

16. A composition comprising a mineral lubricating oil and 0.25 to 25% by weight based upon the oil of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzenoid hydrocarbon sulfonic acid in which the wax substituents do not exceed a total of 3.

17. A composition comprising a mineral lubricating oil and 0.5 to 5% by weight based upon the oil of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzene sulfonic acid in which the wax substituents do not exceed a total of 3.

18. A composition comprising a mineral lubricating oil and 0.25 to 25% by weight based upon the oil of the oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid.

19. A composition comprising a mineral lubricating oil and 0.5 to 5% by weight based upon the oil of the oilsoluble reaction product obtained by reacting substantial ly one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a di-wax substituted benzene sulfonic acid, said wax substituents respectively containing 20 to 30 carbon atoms.

20. The oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt or" a long chain alkyl substituted benzenoid hydrocarbon sulfonic acid in which the long chain alkyl substituents do not exceed a total of 4.

21. The oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a long chain alkyl substituted benzene sulfonic acid in which the long chain alkyl substituents do not exceed a total of 3 and which alkyl substituents respectively contain 8 to 30 carbon atoms.

22. The oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzenoid hydrocarbon sulfonic acid in which the wax substituents do not exceed a total of 3.

23. The oil-soluble reaction product obtained by reacting substantially one molecular proportion of carbon dioxide with substantially two molecular proportions of a basic barium salt of a wax substituted benzene sulfonic References Cited in the file of this patent UNITED STATES PATENTS 2,402,325 Griesinger June 18, 1946 2,417,428 McLennan Mar. 18, 1947 2,480,638 Duncan et al. Jan. 3, 1950 2,493,216 Berger Jan. 3, 1950 2,501,732 Mertes Mar. 28, 1950 2,606,872 Gasser et al. Aug. 12, 1952 2,617,049 Assetf Nov. 4, 1952 2,695,910 Asseif et a1 Nov. 30, 1954 

1. A COMPOSITION COMPRISING A MINERAL OIL FRACTION HAVING IN ADMIXTURE THEREWITH 0.1-40% BY WEIGHT OF AN OIL-SOLUBLE PHOSPHORIZED AND SULFURIZED-DICYCLIC-TERPENE, OBTAINED BY REACTING SUBSTANTIALLY ONE MOL OF A PHOSPHOROUS SULFIDE WITH SUBSTANTIALLY FOUR MOLS OF A DICYCLIC TERPENE AT 100*-160*C., AND 0.1-40% BY WEIGHT OF THE OIL-SOLUBLE REACTION PROCDUCT OBTAINED BY REACTING SUBSTANTIALLY ONE MOLECULAR PROPORTIONS OF CARBON DIOXIDE WTIH SUBSTANTIALLY TWO MOLECULAR PROPORTION OF A BASIC BARIUM SALT OF A LONG CHAIN ALKYL SUBSTITUTED BENZENOID HYDROCARBON SULFONIC ACID IN WHICH THE LONG CHAIN ALKYL SUBSTITUENTS DO NOT EXCEED A TOTAL OF
 4. 10. A FUEL OIL COMPRISING A HYDROCARBON DISTILLATE FUEL HAVING IN ADMIXTURE THEREWITH 0.1-3% BY WEIGHT OF AN OIL-SOLUBLE PHOSPHORIZED- AND SULFURIZED-DICYCLIC TERPENE, OBTAINED BY REACTING SUBSTANTIALLY ONE MOLE OF PHOSPHOROUS PENTASULFIDE WITH SUBSTANTIALLY FOUR MOLS OF A DICYCLIC TERPENE AT 100*-160*C., AND 0.1-10% BY WEIGHT OF THE OIL-SOLUBLE REACTION PRODUCT OBTAINED BY REACTING SUBSTANTIALLY ONE MOLECULAR PROPORTION OF CARBON DIOXIDE WITH SUBSTANTIALLY TWO MOLECULAR PROPORTIONS OF A BASIC BARIUM SALT OF A WAX SUBSTITUTED BENZENE SULFONIC ACID IN WHICH THE WAX SUBTITUENTS DO NOT EXCEED A TOTAL OF
 3. 14. A COMPOSITION COMPRISING A MINERAL LUBRICATING OIL AND 0.25 TO 25% BY WEIGHT BASED UPON THE OIL OF THE OILSOLUBLE REACTION PRODUCT OBTAINED BY REACTING SUBSTANTIALLY ONE MOLECULAR PROPORTION OF CARBON DIOXIDE WITH SUBSTANTIALLY TWO MOLECULAR PROPORTIONS OF A BASIC BARIUM SALT OF A LONG CHAIN ALKYL SUBSTITUTED BENZENOID HYDROCARBON SULFONIC ACID IN WHICH THE LONG CHAIN ALKYL SUBSTITUENTS DO NOT EXCEED A TOTAL OF
 4. 20. THE OIL-SOLUBLE REACTION PRODUCT OBTAINED BY REACTING SUBSTANTIALLY ONE MOLECULAR PROPORTION OF CARBON DIOXIDE WITH SUBSTANTIALLY TWO MOLECULAR PROPORTION OF A BASIC BARIUM SALT OF A LONG CHAIN ALKYL SUBSTITUTED BENZENOID HYDROCARBON SULFONIC ACID IN WHICH THE LONG CHAIN ALKYL SUBSTITUENTS DO NOT EXCEED A TOTAL OF
 4. 